Graphene composite ultra-high molecular weight polyethylene fiber and preparation method thereof

Abstract

The present invention provides a composite ultra-high molecular weight polyethylene fiber and a preparation method thereof, wherein the method comprises mixing glass fiber, graphene slurry, UHMWPE powder and white oil, and then swelling to a molten state, then cooling into a gel-spun, and finally making the fiber from the gel-spun. The method of the present disclosure not only can solve the problem that the glass fiber has poor dispersibility in the case of high viscoelasticity of the ultra-high molecular weight polyethylene, but also can improve the cut resistance of the ultra-high molecular weight polyethylene fiber on the basis of ensuring the flexibility of the yarn.

1 . A composite ultra-high molecular weight polyethylene fiber, wherein the fiber comprises glass fiber and graphene, the glass fiber has a content of 0.2 wt % to 10 wt %, the grapheme has a content of 0.01 wt % to 3 wt %, and the graphene is a single-layer or a multi-layer structure graphene. 
     
     
         2 . The composite ultra-high molecular weight polyethylene fiber according to  claim 1 , wherein the glass fiber accounts for 1 wt % to 6 wt % of the composite ultra-high molecular weight polyethylene fiber, and the graphene accounts for 0.05 wt % of the composite ultra-high molecular weight polyethylene fiber. 
     
     
         3 . The composite ultra-high molecular weight polyethylene fiber according to  claim 1 , wherein the glass fiber has a diameter of 3 μm to 10 μm; the glass fiber has an average length of 30 μm to 100 μm; the glass fiber has a length in the range of 10 μm to 600 μm; the single-layer or multi-layer structure graphene has a sheet diameter of 0.5 μm to 5 μm and a thickness of 0.5 nm to 30 nm; and the single-layer or multi-layer structure graphene has a specific surface area of 200 m 2 /g to 1000 m 2 /g. 
     
     
         4 . The composite ultra-high molecular weight polyethylene fiber according to  claim 1 , wherein the glass fiber has a diameter of 5 μm to 7 μm; the glass fiber has an average length of 50 μm to 70 μm; and the glass fiber has a length in the range of 50 μm to 400 μm. 
     
     
         5 . A method for preparing a composite ultra-high molecular weight polyethylene fiber, comprising:
 Preparing a glass fiber premix: dispersing glass fiber in a first white oil to obtain the glass fiber premix containing 5 wt % to 30 wt % of glass fiber;   Preparing a graphene slurry premix: grinding graphene slurry, filtering, then adding the filter residue to a second white oil, and then adding a first UHMWPE to the second white oil containing the graphene filter residue, heating the premix to a first temperature, raising the first temperature to a second temperature after the same was not bubbled, and maintaining the second temperature.   Preparing a spinning mixture: mixing the glass fiber premix, the graphene slurry premix, a second UHMWPE, an antioxidant, and a third white oil to obtain the spinning mixture;   Swelling and mixing the spinning mixture to form a molten state;   Extruding the spinning mixture which is in the molten state;   Cooling to form a gel-spun; and   Obtaining the composite ultra-high molecular weight polyethylene fiber from the gel-spun.   
     
     
         6 . The method for preparing the composite ultra-high molecular weight polyethylene fiber according to  claim 5 , wherein the glass fiber premix contains 10 wt % to 25 wt % of glass fiber. 
     
     
         7 . The method for preparing the composite ultra-high molecular weight polyethylene fiber according to  claim 5 , wherein the dispersing method for dispersing the glass fiber in the first white oil comprises: first pouring the glass fiber into the first white oil, premixing, and then stirring at a high speed with an emulsifier to form a homogeneous slurry; the emulsifier has a stirring speed of 3000 rpm to 10000 rpm; and a stirring time of 5 min to 60 min. 
     
     
         8 . The method for preparing the composite ultra-high molecular weight polyethylene fiber according to  claim 5 , wherein the glass fiber is modified with a coupling agent, and then used to prepare the glass fiber premix; the specific treatment method for modifying the glass fiber with the coupling agent is as follows: dissolving the coupling agent in anhydrous ethanol, and then the glass fiber is added to mix homogeneously, impregnating, drying, grinding, and filtering by 100 mesh; wherein, the amount of the coupling agent is 0.1% to 3% of the total mass of the glass fiber, and the impregnation time of the glass fiber in the coupling agent ethanol solution is 10 min to 5 h, and the drying temperature is 50° C. to 180° C., and the drying time is 1 h to 6 h. 
     
     
         9 . The method for preparing the composite ultra-high molecular weight polyethylene fiber according to  claim 8 , wherein the coupling agent is a silane coupling agent, and the silane coupling agent is one or a mixture of two or more of A-150, A-151, A-171, KH-550, KH-560, KH-570, KH-580, KH-590, KH-902 or KH-792. 
     
     
         10 . The method for preparing the composite ultra-high molecular weight polyethylene fiber according to  claim 8 , the coupling agent is added in an amount of 0.2% to 2% of the total mass of the glass fiber, the impregnation time of the glass fiber in the coupling agent ethanol solution is 30 min to 2 h, the drying temperature is 80° C. to 130° C., and the drying time is 2 h to 3 h. 
     
     
         11 . The method for preparing the composite ultra-high molecular weight polyethylene fiber according to  claim 5 , wherein the graphene slurry is a mixture of graphene-anhydrous ethanol, the graphene slurry has a graphene concentration of 1 wt % to 8 wt %, and the graphene is a single-layer or multi-layer structure graphene powder. 
     
     
         12 . The method for preparing the composite ultra-high molecular weight polyethylene fiber according to  claim 5 , wherein the graphene slurry has a graphene concentration of 5 wt %. 
     
     
         13 . The method for preparing the composite ultra-high molecular weight polyethylene fiber according to  claim 5 , wherein the single-layer or multi-layer structure graphene has a sheet diameter of 0.5 μm to 5 μm and a thickness of 0.5 nm to 30 nm; and the single-layer or multi-layer structure graphene has a specific surface area of 200 m 2 /g to 1000 m 2 /g. 
     
     
         14 . The method for preparing the composite ultra-high molecular weight polyethylene fiber according to  claim 5 , wherein in the method for preparing the graphene slurry premix,
 the grinding uses a sand mill to grind the graphene-anhydrous ethanol mixture for 3 h to 4 h to a graphene particle size of D99<7 μm, wherein the grinding uses grinding medium of zirconia bead having a particle diameter of 0.6 mm to 0.8 mm, the sand mill has a rotation speed of 1500 rpm to 2800 rpm;   the first UHMWPE is added to the second white oil contained the graphene filter residue under a condition of high-speed stirring, the high-speed stirring has a stirring speed of 1800 rpm to 2000 rpm; and the high-speed stirring has a stirring time of 5 min to 20 min;   the first temperature is 80° C. to 90° C.;   the second temperature is 135° C. to 170° C.;   after heating to the second temperature, the second temperature is maintained for 2.5 h to 4.5 h.   
     
     
         15 . The method for preparing the composite ultra-high molecular weight polyethylene fiber according to  claim 5 , wherein in the method for preparing the graphene slurry premix, the first UHMWPE has a viscosity average molecular weight of (2-6)×10 6  g/mol, the graphene slurry premix has a graphene concentration of 1 wt % to 8 wt %, and the first UHMWPE has a mass fraction of 0.1 wt % to 0.3 wt %. 
     
     
         16 . The method for preparing the composite ultra-high molecular weight polyethylene fiber according to  claim 5 , wherein in the method for preparing the graphene slurry premix, the graphene slurry premix has a graphene concentration of 5 wt % and the first UHMWPE has a mass fraction of 0.2 wt %. 
     
     
         17 . The method for preparing the composite ultra-high molecular weight polyethylene fiber according to  claim 5 , the second UHMWPE has a viscosity average molecular weight of (2-6)×10 6  g/mol and the antioxidant is one or a combination of two or more of antioxidant 1010, antioxidant 1076, antioxidant CA, antioxidant 164, antioxidant DNP, antioxidant DLTP or antioxidant TNP. 
     
     
         18 . The method for preparing the composite ultra-high molecular weight polyethylene fiber according to  claim 5 , wherein in the method for preparing the spinning mixture, the glass fiber premix and the graphene slurry premix are first mixed at a high speed in an emulsifier, then added to a swelling kettle containing the second UHMWPE and the third white oil, and the antioxidant is further added to form the spinning mixture; wherein the second UHMWPE:the third white oil has a mass ratio of 6:94, and the glass fiber in the glass fiber premix:the graphene in the graphene slurry premix:the antioxidant has a mass ratio of (0.2-10):(0.01-3):(0.01-1). 
     
     
         19 . The method for preparing the composite ultra-high molecular weight polyethylene fiber according to  claim 18 , wherein the glass fiber in the glass fiber premix:the graphene in the graphene slurry premix:the antioxidant has a mass ratio of (1-6):(0.05):(0.1-0.5). 
     
     
         20 . The method for preparing the composite ultra-high molecular weight polyethylene fiber according to  claim 1 , wherein the swelling is carried out by heating to 100° C. to 140° C. in a swelling kettle and holding for 1 h to 3 h.